Optical properties of bilayer quantum dot models based on coronene and its BN analogues with a BODIPY dye: Theoretical TD-CAM-B3LYP-D3 investigation

Quantum dots (QD) belong to a class of materials considered technologically important for their tunable absorption and emission properties and a huge application potential in optoelectronic technologies. To date, only simplified monolayer models of QDs and their dimers have been considered when modeling their absorption and/or emission spectra and effects of edge functionalization. Here, we analyze the optical properties of new type electron donor-acceptor bilayer quantum dot models based on coronene and its boron-nitride analogues (electron donors) with a 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene dye (Bdp, an electron acceptor) dye by using time-dependent density functional theory. To understand the nature of transition shifts in electronic spectra, we use BN models with strong modification of the HOMO and LUMO: m-BNC (middle hexagonal ring CC bonds are substituted by BN), p-BNC (all peripheral CC bonds are substituted by BN), and f-BNC (all C atoms are replaced by B and N in an alternate manner). Adiabatic ionization potentials of all coronenes were also calculated. The obtained results show that significant interlayer charge transfer (CT) on excitation of bilayer QDs in S-1, S-2, and S-3 states from strong electron donors, coronene (6.93 eV) and m-BNC (6.52 eV), to Bdp will occur. As a result, one can observe only very weak absorption of CT-character in the low-energy spectrum region as well as strong fluorescence quenching of Bdp. On the contrary, for the weak electron donors, p-BNC (7.22 eV) and f-BNC (8.22 eV), strong Bdp-like absorption and fluorescence bands of local excitation character in the low-energy region are expected. Correlation of optical properties of bilayer QDs with ionization potentials of coronene monolayers has been founded. The obtained results can be useful for future graphene-based optoelectronic applications. (C) 2018 Elsevier B.V. All rights reserved.